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• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
  • C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
  • C08H1/00—Macromolecular products derived from proteins
  • C08H1/06—Macromolecular products derived from proteins derived from horn, hoofs, hair, skin or leather
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L97/00—Compositions of lignin-containing materials
  • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/20—Diluents or solvents
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/43—Thickening agents
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/45—Anti-settling agents
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
  • C09K3/22—Materials not provided for elsewhere for dust-laying or dust-absorbing
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
  • C09K8/02—Well-drilling compositions
  • C09K8/04—Aqueous well-drilling compositions
  • C09K8/14—Clay-containing compositions
  • C09K8/18—Clay-containing compositions characterised by the organic compounds
  • C09K8/20—Natural organic compounds or derivatives thereof, e.g. polysaccharides or lignin derivatives
  • C09K8/206—Derivatives of other natural products, e.g. cellulose, starch, sugars
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3788—Graft polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L97/00—Compositions of lignin-containing materials
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L97/00—Compositions of lignin-containing materials
  • C08L97/005—Lignin

Definitions

• the present invention relates to the use of Lignin graft polymers with improved biological Degradability as a building block in condensation resins, as binding and Agglomerating agents, as polymers that absorb aqueous and organic liquids, as Flocculant, as a thickener, as an aid in oil drilling (Drilling fluids) and promotion, as suspending and dispersing agents and as Aids in textile and fiber finishing.
• Lignin is a high molecular substance that occurs in woody plants and in which Obtaining cellulose as a minor component. Depending on the type of wood, the molecular one
• the structure of the lignin is different, i.e. the phenylpropane structure varies in the Number of methoxy and hydroxy groups. Only a small proportion of the lignin is water-soluble, the much larger, water-insoluble part can with solvents such as for example, acetone or dioxane can be extracted.
• the technical production runs in the The main thing about the alkali or sulfite digestion of wood, in which the water-soluble Alkali or lignin sulfonates are obtained as well as via the Organosolv process, in which the lignin is extracted from the wood using a solvent / water mixture.
• the Molecular weights of the lignin range from 1000 to 150,000
• No. 4,687,828 describes high-molecular lignin graft polymers which are polar.
• aprotic solvents using the monomers acrylamide and Acrylamidomethylpropanesulfonic acid can be produced in a nitrogen atmosphere
• Initiator system is a combination of calcium chloride, sulfuric acid, cerium (IV) salt and Auto-oxidation products of dioxane (hydroperoxides) used. After a response time the polymer is precipitated in a non-solvent for 2 days at 30 ° C. and separated off Polymers with an increased purity and better solubility are obtained by Redissolve in water, dialyze for several days and freeze-dry.
• the degree of grafting is not made, but the examples show that only about 40 % Of the amount of lignin used is recovered, the loss of monomer is within the scope of the loss of yield of approx. 80%. Other types of monomers will be not applied according to this procedure.
• the graft polymers are for use as Thickeners, flood polymers and drilling fluid additives are proposed.
• EP 442 508 A 1 is a process for the production of graft polymers from lignin or Wood pulps containing lignin and unsaturated acrylate or methacrylate monomers remove that the graft reaction in a solvent in the absence of oxygen in Presence of halogen salt and a hydrogen peroxide initiator.
• Grafting should be obtained from fillers / reinforcing materials compatible with plastics become.
• WO 94/01488 teaches a method for the enzymatic polymerization / modification of Materials containing lignin or lignin in water with peroxidase and hydrogen peroxide at alkaline pH values without using organic solvents.
• the so modified lignins have a higher molecular weight and are used as binders for Chipboard used. Polymerization in the presence of synthetic monomers is not described.
• the object is surprisingly achieved in that the oxidizing enzymes catalyzed graft polymerization on lignin in the presence of organic Peroxides / hydroperoxides.
• the oxidizing enzymes catalyzed graft polymerization on lignin in the presence of organic Peroxides / hydroperoxides.
• there is neither Damage to the enzymes caused by the organic peroxides leads to an increase in the Homopolymer portion, as can be expected when adding peroxidic initiators. It is a significant increase compared to the use of hydrogen peroxide or oxygen the polymerization yield and the proportion of the grafted monomer increases in the graft polymer.
• the yield of graft polymer according to the inventive method is high and lies preferably over 50% by weight, particularly preferably over 60% by weight and very particularly preferably over 75% by weight.
• the graft polymers have an unexpected biodegradability on, which results in a decrease in molecular weight after exposure to white rot causing basidomycetes. After an incubation period of 48 days, through biodegradation reduces the molecular weights by at least 50%.
• organic peroxides in the enzymatic grafting has proven itself for the Increasing the graft yield was found to be crucial. Your solubility in the Assuming the solvent or solvent mixture used, the organic peroxides based on the monomers used in amounts of 0.01% by weight to 10% by weight, preferably from 0.1% by weight to 5% by weight and particularly preferably from 0.25% by weight up to 1.5% by weight.
• Organic aliphatic, cycloaliphatic to be mentioned as examples and aromatic peroxides are t-butyl hydroperoxide, mono- and dihydroxyperoxides Dioxane, acetylcyclohexanesulfonyl peroxide, diacetyl peroxidicarbonate, Dicyclohexyl peroxide carbonate, di-2-ethylhexyl peroxidicarbonate, tert-butyl perneodecanoate, tert-butyl perpivalate, dioctanoyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, tert-butyl per-2-ethyl hexanoate, tert-butyl permaleinate, bis (ter-butyl peroxide) cyclohexane, tert-butyl peroxy isopropyl carbonate, tert-butyl peracetate, 2,2'-bis
• redox coinitiators can have a positive influence on the polymer and graft yield.
• the heavy metal salts of copper, cobalt, iron, manganese, nickel and chromium may be mentioned by way of example, with Fe 2+ and Mn 2+ having proven particularly useful.
• Reducing components such as ascorbic acid, sodium sulfite, sodium bisulfite, sodium formaldehyde sulfoxylate lead to a significant reduction in the polymerization activity.
• the use of redox coinitiators allows the polymerization to be carried out at a lower temperature.
• the amounts of redox coinitiators usually used are about 0.01 to 5% for reducing compounds and 0.1 to 100 ppm, preferably 0.5 to 10 ppm for heavy metals.
• the lignin-modifying enzymes to be used consist of oxidases, such as laccases, lignin peroxidases, Mn peroxidases or mixtures thereof. Laccases are preferably used.
• the use concentration of the enzymes can be in fluctuate wide boundaries and according to the type of enzyme and used Initiator system and the number of phenoxy radicals to be generated. based on the Monomers used have guideline concentrations of 200 to 0.1 U per g of monomer, preferably from 100 to 1 U per g of monomer and particularly preferably from 25 to 1 U per g Monomer.
• the enzyme unit U is defined as the amount of enzyme that is 1 mmol per minute Implement substrate.
• Enzyme matrix complexes are included.
• enzyme-matrix complexes and their Production is described in EP 354 485.
• Lignin, lignin derivatives and materials containing lignin are used as the graft base used, especially the lignins and ligninsulfonates of various vegetable origin and molecular weight.
• Ullmann's Encylopedia of Industrial Chemistry (5th Ed., 1990, Vol. 15) contains an overview of lignins that are also within the scope of the invention Grafting can be used. Due to the sulfonate groups, the Graft polymers based on lignin sulfonates have improved solubility in water compared to products based on sulfonate-free lignins.
• the spectrum ranges from low molecular weight Crystallization inhibitors for hard water components up to high molecular flocculation and Thickeners as well as cross-linked superabsorbers, lignins are different Molecular weight used for grafting.
• the proportion of the lignin component in the monomer mixture can be within wide limits fluctuate, but should not exceed 50%, since this leads to lower yields and Molecular weights leads. It is to achieve high molecular weights of over 200,000 often advantageous, the amount of lignin not more than 25% by weight, preferably not more than 15 % By weight and particularly preferably not to rise above 10% by weight.
• the addition of surfactants to the lignin derivative in question To make the graft reaction accessible.
• the selection of the surfactant (s) depends on the one hand according to the structure of the lignin component and on the other hand according to the composition of the Reaction medium and is carried out according to methods familiar to those skilled in the art.
• the properties of use of pre-crosslinked graft polymers can be determined significantly improve post-networking.
• this post-networking can be used by everyone Moisture contents of the pre-crosslinked polymer gel are carried out.
• the drying of the polymer gel takes place up to a Water content of 5-20% by weight, preferably at most 10% by weight at temperatures in the Range from 100 - 190 ° C.
• the dry material is then cut to a grain size in the range from 20 - 3000 ⁇ m, preferably 150 - 850 ⁇ m, ground to polymer powder.
• Post-crosslinking of the polymer takes place on the surface of the polymer particles with at least one, two or more functional groups with acid groups, preferably carboxyl groups, reacting crosslinking agent, preferably in the form of an aqueous solution is applied.
• Post-crosslinking agents are polyols such as ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, glycerol, di- and polyglycerol, pentaerythritol, the oxyethylates these polyols and their esters with carboxylic acids or carbonic acid are suitable.
• an esterification catalyst e.g. B. p-toluenesulfonic acid or phosphoric acid is advantageous.
• crosslinking agents are di- and polyglycidyl ethers of polyols and Polyethylene glycols and salts of polyvalent cations.
• the post-crosslinkers are in Amounts of 0.01 to 20% by weight, preferably 0.1 to 10 and particularly preferably 0.1 to 3 % By weight based on the polymer used.
• Post-crosslinking is usually carried out at temperatures in the range from 100 to 250 ° C. preferably 150-200 ° C in a mixing unit, for example in a Naramischer performed. Very reactive postcrosslinkers can also be used at lower temperatures of 20 up to 100 ° C. Post-crosslinking is often also carried out in inert solvents suspended graft polymer particles. The use of various post-crosslinkers or multiple post-networking is possible.
• Monomers bearing acid groups are used and are particularly preferred Embodiment acrylic acid and methacrylic acid, whereas superabsorbent polymers in plant cultivation additionally acrylamide, methacrylamide and sulfonate groups Have monomer components.
• Flocculants and dispersants are both based on prepared anionically as well as on cationic monomer basis, as comonomer is preferred Acrylamide used.
• the in the field of water softening and washing and Polymers used for cleaning agents are preferably predominantly made of Monomers containing carboxylate groups, but have also proven successful here Comonomers containing sulfonate and alkoxylate groups.
• inorganic per compounds are added as long as they do not interfere with the grafting reaction or significantly reduce the grafting yield.
• the addition of inorganic peroxides towards the end of the Polymerization sustainably reduces residual monomer levels, causing others elaborate processes for their separation can be omitted.
• Be particularly advantageous these per compounds activated by adding reducing compounds.
• Sodium peroxodisulfate, potassium peroxodisulfate, ammonium peroxodisulfate, peroxyborate Examples of inorganic per-compounds to be used.
• azo initiators can also be used favorably use.
• the following azo initiators are an exemplary list of Initiators which can be used according to the invention: 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis - ((2-methyl-N-phenylpropionamidine) dihydrochloride, 2,2'-azobis (2-methylpropionamidine) dihydrochloride, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (isobutyronitrile), Dimethyl-2,2'-azobisisobutyrate.
• the inventive method is in water, org. Solvents or Water / solvent mixtures carried out.
• solvent components come under other dimethyl sulfoxide, acetone, dioxane, methylpyrrolidone or mixtures thereof.
• water / solvent mixtures that is correct Mixing ratio of water to solvent, of course, also according to the miscibility of the two Components.
• a water content of more used as 50 wt.% is particularly preferred. Solvents.
• the graft polymerization can be carried out in normal polymerization reactors using appropriate aggregates for stirring, dosing solid, liquid and gaseous substances, for Heating and cooling are equipped.
• the graft base is in the reactor together with submitted to the enzyme and then immediately or in the course of the polymerization with the Monomer components added. It is often an advantage to start with a small portion of the Submit monomers and meter the rest over a long period.
• other polymerization devices such as reaction mixers or polymerization belts.
• the temperatures at the enzymatic polymerization are due to the temperature stability of the enzyme and limited by the activity of the enzyme or the rate of polymerization.
• Preferred ranges of the polymerization temperature are between 10 and 60 ° C particularly preferably between 20 and 50 ° C.
• the polymerization time can vary depending on the activity of the enzyme, the phenol component, the monomers and the graft polymerization temperature fluctuate between 1 h and 2 days.
• a protective gas atmosphere may be required during the polymerization in order to prevent free radicals Avoid chain breaks.
• the pH during the graft polymerization according to the invention can be in a range of 3 to 8, preferably from. 4 to 5 fluctuate.
• the time of neutralization of the Monomer components depend on the required pH of the Graft polymerization solution and can therefore before, during or after the polymerization lie or take place continuously or discontinuously in partial steps.
• Neutralizing agents can be inorganic and organic bases and acids, for example ammonia, ammonium hydroxide, alkali hydroxides, carbonates and hydrogen carbonates, amines, alkylamines, alkanolamines, hydroxylamine, mineral acids, organic sulfonic acids.
• the batch concentration during the graft polymerization can fluctuate and depends, among other things. depends on whether high or low molecular weights are to be produced, whether high or low levels of monomer are present, whether cross-linked or soluble graft polymers are produced should be or whether water, org. Solvents or mixtures of water with org. Solvents are used as the reaction medium. In any case, it should be noted that the batch concentration is designed so that the required optimal Graft polymerization temperature can be maintained.
• the graft polymers show more or less pronounced coloring, which may be mitigated by oxidative or reductive additives or can be eliminated.
• Hydrogen peroxide, sulfite salts or phosphorous acid proven for bleaching.
• the soluble polymers are either directly Application supplied, or for special requirements by removing the Solvent (spray drying / evaporation / freeze drying) or by precipitation as a powder isolated.
• the precipitation can be done by adjusting the pH and / or by adding Not solvents.
• dialysis has been removed Proven low molecular weight. Dialysis membranes with different exclusion limits are available for purchase.
• the polymerization can also take the form of a suspension polymerization be carried out, the aqueous reaction phase with the aid of Suspension stabilizers in an organic phase, the z. B. can consist of cyclohexane, is dispersed and polymerized in the form of this suspension. After that, the water Distilled off azeotropically from the suspension and the solid polymer particles can easily filtered off from the organic phase and, after drying, fed to their use.
• Crosslinked graft polymers are comminuted after or during the polymerization. domed, dried and according to their intended use to a specific Particle size ground.
• the molecular weight averages of the graft polymers can be influenced within wide limits range between 1000 and 10 million due to application requirements Different molecular weights required for different areas of application. So be for example in the field of flocculation and thickening aids very high molecular weight Polymers are used, for water softening, dispersion and drilling fluid Polymers according to the invention with comparatively low molecular weights are used.
• the essential control parameters for the molecular weight are on the one hand Molecular weights of the graft base and on the other hand the enzyme / monomer ratio.
• the graft polymers are advantageous in many fields of application used.
• the absorption of aqueous and organic liquids, the targeted release of previously absorbed substances (controlled release), the flocculation, the Water softening, dispersion, thickening and agglomeration called.
• cross-linked ones are used Polymers that swell when absorbing the liquids and the absorbed Save liquid.
• the amount of crosslinking agents and, if necessary, postcrosslinking can do this Absorption behavior of the polymers can be controlled, especially that Absorption behavior under load, which is necessary for the use of the products in diapers Meaning is.
• acidic monomers hydrophilic, water and aqueous liquids, especially blood and urine absorbing Polymers for use in the hygiene sector are particularly suitable because, in contrast to the purely synthetic absorbers, they are organic are degradable.
• the absorbent polymers can also, after adding active ingredients to them, hand it over after a long period of time. For example, additions from Called insecticides or fertilizers, which have a longer lasting sustainable control of the insects or the independent supply of nutrients to the Plants over a longer period of time. This is also particularly advantageous Applications that the absorbers end up after their use subject to biodegradation.
• the polymers become soluble Form used, in particular high molecular weights of over 1 million preferred are.
• Typical flocculation processes take place on municipal wastewater, for example industrial waste water, in chemical / technical processes, for example in the Red mud flocculation or paper production and drinking water treatment carried out.
• the Polymers through the selection of the monomer components to be polymerized have an anionic, cationic or amphoteric character.
• the polymers are used as flocculants, depending on the flocculation process, in concentrations of 0.1 to 5000 ppm, preferably 0.1 to 1500 and particularly preferably from 0.1 to 500 ppm.
• detergents and cleaning agents come with their good complexing properties polyvalent ions such as calcium, iron and magnesium and on the other hand you good dispersibility. The latter keeps contaminants and fancy Hard water components in suspension during the washing process. These properties also enable the advantageous use of the polymers in the fiber and Textile treatment, especially in bleaching and dyeing baths and when preparing the Raw fibers and desizing, where there is also complexation of heavy metals and the dispersion of hard water components, accompanying substances of raw fibers and excess color pigments.
• the polymers are used in water cycles Prevention of hard water precipitation used.
• Detergents and cleaning agents included usually 0.1 to 20% by weight, preferably 0.5 to 12% by weight of the Polymers. For water softening, polymer concentrations of 0.2 to 5000 ppm, preferably 1 to 2000 ppm applied. In the textile treatment, 0.1 to 10, preferably 0.1 to 5 g of polymer per liter of liquor added.
• the good dispersing properties of the polymers according to the invention also become Production and stabilization of dispersions of organic color pigments and inorganic Pigments (e.g. titanium dioxide, calcium carbonate, talc) are used and for the dispersion of drilling muds that occur during drilling.
• organic color pigments and inorganic Pigments e.g. titanium dioxide, calcium carbonate, talc
• the dispersion of organic color pigments and inorganic pigments usually require 1 to 20% by weight polymer based on Pigment, where the ratio of polymer to organic color pigment varies in some Extreme cases can also be 1: 1.
• Molecular weights of the polymers are in the range below 100,000, preferably below 50,000 and very particularly preferably below 25,000.
• polymers as thickeners for water and aqueous Preparations used, for example in printing inks, paper coating slips, paint dispersions or in the tert. Oil production, so high molecular weight polymers are preferred, i.e. the Molecular weights should preferably be over 1 million for good Thickening performance occurs. In pigment printing, for example, up to 10 g of polymer per Liters of printing paste used and in oil production up to 1000 ppm.
• the polymers are also suitable as binders or agglomerating agents.
• binders or agglomerating agents For example, the agglomeration of filter dust, soot, fine coal, ballast coal and other dusts and powders and the setting of wood materials and Core sands (foundry).
• the biodegradability of the graft polymers is surprising because according to the knowledge of the prior art, both the synthetic graft branches as well as the phenolic graft bases, especially the lignin, as non-degradable were classified.
• the degradability of the graft polymers was influenced by Basidomycetes that cause white rot are investigated and compared with the reduction of the Molecular weight detected.
• laccase is an example of the group of using oxidizing enzymes. It is an enzyme from Novo, Denmark. The enzyme activity is about 190U / mL. As the enzyme unit U is that Defines the amount of enzyme that converts 1 mmol substrate per minute.
• the molecular weights were determined by gel permeation chromatography. Pullulan standards were used as molecular weight standards. The following molecular weight averages were obtained from the chromatograms: Mn: number average, Mw: weight average, Mp: molecular weight at the peak of the elution curve.
• Mn number average
• Mw weight average
• Mp molecular weight at the peak of the elution curve.
• the comparative example is identical to example 4 of DE 43 31 878 A1.
• a total of 937 mg of polymer were obtained from the 0.4 g of organosolvlignin and 3.2 g of acrylamide using the laccase / oxygen initiator system.
• the yield in this comparative example was therefore 26%.
• Bsp.5 4.0 ml acrylic acid 400 mg
• Wafex SR sulfonate lignin with approx.
• sulfonate lignin 22 ml of acrylic acid and 230 mg of methylene bisacrylamide (MBAA) were distilled in 200 ml. Dissolved water and adjusted to pH 4 with sodium hydroxide solution. 15 mg (NH 4 ) 2 Fe (SO 4 ) 2 .6 H 2 O (Mohr's salt) were then dissolved in 1 ml bidistilled. Pipetted water and 1 ml of laccase and started the reaction by adding 400 ul t-butyl hydroperoxide. The reaction mixture was kept in a water bath at 35 ° C. for 48 h. After a reaction time of 2 days, the polymer was dried in a drying cabinet at 80 ° C.
• MBAA methylene bisacrylamide
• the preparation is carried out analogously to Ex. 14, but with 185 mg MBAA.
• water-insoluble sulfate lignin (indulin) was used without subsequent sulfonation.
• in order to increase the accessibility of the lignin molecule it was first dissolved in 140 ml of 0.01 N sodium hydroxide solution and 16.6 g of acrylamide, 11.4 ml of trimethacryloylamidopropylammonium chloride (60% solution) and 1 ml of Tween 80 were added. The pH was then adjusted to 5 by slow titration with 0.1 N hydrochloric acid. The lignin forms a voluminous suspension.
• the degradability of the investigated polymers was determined by reducing the Molecular weight of the synthesized polymers examined. There were different ones Graft polymers based on lignin / acrylic acid and these in liquid cultures Subjected to white rot-causing basidomycetes. With the selected one Strain it was Pleurotus ostreatus.
• Liquid cultures The liquid cultures were first grown in three 500 ml Erlenmeyer flasks with 100 ml medium. The inoculation was carried out with three 1 cm 2 pieces of malt agar from the stock culture, the incubation time was three weeks in the dark culture room at 23 ° C.
• 0.5 g polymer was dissolved in 100 ml of the corresponding medium per Erlenmeyer flask, using three parallels per polymer species. After autoclaving and In each case 1 ml of the polymer solution for the molecular weight determination was cooled by HPLC (GPC). The three-week-old liquid cultures were made using a Turrax rod homogenized and 1 ml of the resulting suspension pipetted into the polymer solutions. The Incubation took place over a period of 48 days in the dark culture room at 23 ° C. After 1 ml of the culture medium was again removed and the molar mass of the contained polymer determined.
• Lignin component For lignin-acrylic acid graft polymers, the following changes in molecular weight resulted from the biodegradation: Lignin component, proportion in the graft polymer Molecular weight before incubation after 48 days % Decrease Lignin sulfonate [5%] 325 810 151 379 53.5 Lignin sulfonate [10%] 254 509 99 281 61.0 Lignin sulfonate [20%] 175 159 58 172 66.8 Lignin sulfonate [30%] 128 964 45 665 64.6
• the retention capacity of the crosslinked polymers for aqueous liquids is determined for a 0.9% saline solution. After the polymers have dried, ground and simmered to 180 to 800 ⁇ m, the test is carried out as follows: 200 mg of test substance are sealed in a tea bag and immersed in a 0.9% NaCl solution for 30 minutes, drained for 10 minutes and spun in a centrifuge (23 cm diameter, 1400 rpm) for 5 minutes and weighed.
• a solution of 1 g of product (dry substance) in 100 ml of water is mixed with 2 ml of 10% sodium carbonate solution and adjusted to pH 11 with sodium hydroxide solution. Titrate with 0.25mol calcium acetate solution until the first permanent turbidity occurs.
• the information is given in mg CaCO 3 / g dry substance: example Hampshire value [mg CaCO 3 / g TS] 18 1328 Maleic / acrylic acid copolymer 590
• the polymers according to the invention show excellent calcium binding capacity Hampshire, which is significantly above the commercially available synthetic copolymers, which as Cobuilder can be used for detergents.
• a certain amount of 10% polymer solution is added to a calcium chloride solution (33.6 ° dH pure calcium hardness), heated on a hot plate for 5 minutes and then assessed for turbidity.
• the concentration at which a clear solution is obtained for the first time is determined by varying the amount of polymer.
• the specification is made in grams of polymer per liter of hard water. example Hard water resistance [g polymer / l] 1 2.0 2 1.0 16 0.5 Maleic acid / acrylic acid copolymer 2.0
• the flocculation effect of the polymers according to the invention is measured on a blue clay suspension produced in the laboratory.
• This suspension consists of 18 g blue in 11 water and is suspended with a high-speed stirrer and transferred to a 250 ml test cylinder with a diameter of 5 cm. There, stirring is continued with a slow finger stirrer and 2.5 ml of 20% aluminum sulfate solution are added. 20 or 2 seconds later, 2 or 4 ppm of flocculant polymer are added and after a further 5 seconds the stirrer is switched off.
• the flocculation value is then measured as the time the surface of the flocculated blue clay suspension sinks between two 4 cm apart markings in the middle of the cylinder. example Flocculation time [sec] 2 ppm polymer Flocculation time [sec] 4 ppm polymer 19 42.8 33.4

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• 1997
  • 1997-12-17 DE DE19756172A patent/DE19756172A1/de not_active Withdrawn
• 1998
  • 1998-12-17 CA CA002330117A patent/CA2330117A1/fr not_active Abandoned
  • 1998-12-17 AU AU21626/99A patent/AU2162699A/en not_active Abandoned
  • 1998-12-17 EP EP98965847A patent/EP1040145B1/fr not_active Expired - Lifetime
  • 1998-12-17 WO PCT/EP1998/008279 patent/WO1999031155A1/fr not_active Ceased
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• 2000
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